This is a continuation-in-part of application Ser. No. 07/054,656, filed May 27, 1987, incorporated herein by reference.
Disclosed herein are cyclopentanedioxocarbonyl vinylene polymers, methods of preparing such polymers from norbornene dioxocarbonyl and uses for such polymers.
As used herein the term "norbornene dioxocarbonyl" refers to 5,6-dioxycarbonyl 2.2.1] bicyclohept-2-ene which is prepared as the Diels-Alder adduct of cyclopentadiene and vinylene carbonate and which is identified as a substantially endo stereoisomer of the following structure ##STR1## The term "endo" refers to the stereoisomer form of a monomer such as norbornene dioxocarbonyl in which the oxygen atoms and the double bond are both on the same side of the surface of the saturated five-membered ring of the monomer unit. Conversely, the term "exo" refers to the stereoisomeric form of such monomer units in which the oxygen atoms and the double bond are on opposite sides of the surface of the saturated five-membered ring of the monomer unit.
Feast et al. in Journal of Molecular Catalysis, 28, (1985) page 293, reported no success in preparing the homopolymer of the endo stereoisomer of norbornene dioxocarbonyl through metathesis ring-opening polymerization. Feast et al. did report limited success in copolymerizing norbornene with low levels (about 8%) of norbornene dioxocarbonyl and also speculated that the exo stereoisomer might be more readily polymerizable than the endo stereoisomer. In this regard it is believed that attempts to produce the exo stereoisomer by high temperature isomerization, e.g. by heating, will be generally unsuccessful with norbornene dioxocarbonyl because during such isomerization the shock-sensitive, e.g. unstable, vinylene carbonate will be generated.
Milner in British Patent Specification No. 1,546,775 claims a variety of norbornene polymers including polymers having monomer units of norbornene diol. However, Milner teaches only the production of the polymer of the mono hydroxyl substituted norbornene by hydrolysis of the mono ester, i.e. polynorbornene acetate.
Ueda et al. in U.S. Pat. 4,166,083 state that the polymers of an acetic acid ester of 5-norbornene-2,3-diol can be prepared by methods disclosed by Michelotti et al. J. Polymer Sci, 3, 895-905 (1965) which is limited to teaching the polymerization of norbornene and chloromethyl norbornene. Michelotti et al. failed to polymerize norbornene nitrile. Since there is no teaching of a generalized polymerization procedure for norbornene derivatives, Ueda et al. do not provide any enablement for the polymer of the diester of norbornene diol.
McKeon et al. in U.S. Pat. No. 3,330,815 disclose polymers of a variety of bicyclo norbornene derivative monomer units, e.g. 5,6-dihydroxybicyclo [2.2.1] hept-2-ene (referred to herein as norbornene diol) and the diesters. Such polymers are produced through a vinyl-type addition polymerization and not a metathesis ring opening polymerization.